Synergistic stabilizer mixture

ABSTRACT

Stabilizer mixture comprising, for example, a compound of the formula ##STR1## and, for example, a compound of the formula ##STR2##

The present invention relates to a stabilizer system comprising twospecific polyalkylpiperidine derivatives, some of which are novel, tothe use of this stabilizer system for stabilizing organic material, andto the organic material protected against thermal, oxidative orlight-induced degradation by means of the stabilizer system mentioned.

Polyalkylpiperidine derivatives are described for example in WO-A-94/12544, U.S. Pat. No. 4,110,334 and U.S. Pat. No. 5,204,473.

U.S. Pat. No. 4,692,486, U.S. Pat. No. 4,863,981, U.S. Pat. No.4,957,953, WO-A-92/12 201, WO-A-94/22 946, EP-A-449 685, EP-A-632 092,GB-A-2 267 499 and Research Disclosure 34 549 (January 1993) describesome stabilizer mixtures which comprise two polyalkylpiperidinederivatives.

The present invention relates to a stabilizer mixture comprising acomponent I-a), I-b), I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j),I-k) or I-l) and a component II-a), II-b), II-c), II-d), II-e), II-f),II-g), II-h), II-i), II-j), II-k), II-l) or II-m), where

component I-a) is at least one compound of the formula I-1 ##STR3## inwhich R₁ is hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or C₁ -C₄alkyl-substituted C₅ -C₁₂ cycloalkyl,

n₁ is 1, 2 or 4,

if n₁ is 1, R₂ is C₁ -C₂₅ alkyl,

if n₁ is 2, R₂ is C₁ -C₁₄ alkylene and

if n₁ is 4, R₂ is C₄ -C₁₀ alkanetetrayl,

with the provisos that,

(1) in a stabilizer mixture comprising component I-a) and componentII-b) or II-m), if n₁ =2, R₁ is other than C₁ -C₁₈ alkyl and

(2) in a stabilizer mixture comprising component I-a) and componentII-d), if n₁ =2 and R₁ =C₁ -C₁₈ alkyl, the group --N(A₁₄)A₁₅ is a 5- to10-membered heterocyclic ring;

component I-b) is at least one compound of the formula II-1 ##STR4## inwhich R₃ and R₇ independently of one another are hydrogen or C₁ -C₁₂alkyl,

R₄, R₅ and R₆ independently of one another are C₂ -C₁₀ alkylene and X₁,X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are a groupof the formula III-1 ##STR5## in which R₈ is hydrogen, C₁ -C₁₂ alkyl, C₅-C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl, phenyl,--OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇ -C₉ phenylalkyl, C₇-C₉ phenylalkyl which is substituted on the phenyl radical by --OHand/or C₁ -C₁₀ alkyl, or is a group of the formula IV-1 ##STR6## and R₉and R₁₀ independently of one another are as defined for R₁ ;

component I-c) is at least one compound of the formula V-1 ##STR7## inwhich X₉, X₁₀ and X₁₁ independently of one another are a group of theformula III-1;

component I-d) is at least one compound of the formula VI-1 ##STR8## inwhich R₁₁, R₁₃, R₁₄ and R₁₅ independently of one another are hydrogen,C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂cycloalkyl, phenyl, --OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇-C₉ phenylalkyl, C₇ -C₉ phenylalkyl which is substituted on the phenylradical by --OH and/or C₁ -C₁₀ alkyl, or are a group of the formulaIV-1,

R₁₂ is C₂ -C₁₈ akylene, C₅ -C₇ cycloakylene or C₁ -C₄ alkylenedi(C₅ -C₇cycloalkylene), or the radicals R₁₁, R₁₂ and R₁₃, together with thenitrogen atoms to which they are attached, form a 5- to 10-memberedheterocyclic ring, or

R₁₄ and R₁₅, together with the nitrogen atom to which they are attached,form a 5- to 10-membered heterocyclic ring,

n₂ is a number from 2 to 50 and

at least one of the radicals R₁₁, R₁₃, R₁₄ and R₁₅ is a group of theformula IV-1;

component I-e) is at least one compound of the formula VII-1 ##STR9## inwhich R₁₆ is C₁ -C₁₀ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substitutedC₅ -C₁₂ cycloalkyl, phenyl or C₁ -C₁₀ alkyl-substituted phenyl,

R₁₇ is C₃ -C₁₀ alkylene,

R₁₈ is as defined for R₁ and

n₃ is a number from 1 to 50;

component I-f) is a product obtainable by

a) reacting a product, obtained by reaction of a polyamine of theformula VIII-1-a with cyanuric chloride, with a compound of the formulaVIII-1-b ##STR10## in which n₄ ', n₄ " and n₄ '" independently of oneanother are a number from 2 to 12 and

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, phenyl or C₇ -C₉phenylalkyl, and

b) further reacting the 2,2,6,6-tetramethylpiperid-4-yl groups presentin the molecule to give groups of the formula VII-1-c ##STR11## in whichR₂₀ is as defined for R₁ ; component I-g) is at least one compound ofthe formula IX-1 ##STR12## in which R₂₁ and R₂₆ independently of oneanother are a direct bond or a group --N(Y₁)--CO--Y₂ --CO--N(Y₃)--,

Y₁ and Y₃ independently of one another are hydrogen, C₁ -C₈ alkyl, C₅-C₁₂ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formulaIV-1,

Y₂ is a direct bond or C₁ -C₄ alkylene,

R₂₂ is as defined for R₁,

R₂₃, R₂₄, R₂₇ and R28 independently of one another are hydrogen, C₁ -C₃₀alkyl, C₅ -C₁₂ cycloalkyl or phenyl,

R₂₅ is hydrogen, C₁ -C₃₀ alkyl, C₅ -C₁₂ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV-1 and

n₅ is a number from 1 to 50;

component I-h) is at least one compound of the formula X-1 ##STR13## inwhich R₂₉ is C₁ -C₂₄ alkyl and

R₃₀ is as defined for R₁ ;

component I-i) is at least one compound of the formula XI-1 ##STR14## inwhich R₃₁ is as defined for R₁ and

n₆ is a number from 2 to 50;

component I-j) is at least one compound of the formula XII-1 ##STR15##in which R₃₂ and R₃₃ together form C₂ -C₁₄ alkylene,

R₃₄ is hydrogen or a group --Z₁ --COO--Z₂,

Z₁ is C₂ -C₁₄ alkylene and

Z₂ is C₁ -C₂₄ alkyl and

R₃₅ is as defined for R₁ ;

component I-k) is at least one compound of the formula XIII-1 ##STR16##in which R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ independently of one another are adirect bond or C₁ -C₁₀ alkylene,

R₄₁ is as defined for R₁ and

n₇ is a number from 1 to 50;

component I-l) is at least one compound of the formula XIV-1 ##STR17##in which X₁₂, X₁₃ and X₁₄ independently of one another are a group ofthe formula XV-1 ##STR18## in which A is a group of the formula III-1;component II-a) is at least one compound of the formula I-2 ##STR19## inwhich A₁ is hydrogen, C₁ -C₈ alkyl, O, --CH₂ CN, C₃ -C₆ alkenyl, C₇ -C₉phenylalkyl or C₇ -C₉ phenylalkyl which is substituted on the phenylradical by C₁ -C₄ alkyl,

b₁ is 1, 2 or 4,

if b₁ is 1, A₂ is C₁ -C₂₅ alkyl,

if b₁ is 2, A₂ is C₁ -C₁₄ alkylene and

if b₁ is 4, A₂ is C₄ -C₁₀ alkanetetrayl;

component II-b) is at least one compound of the formula II-2 ##STR20##in which A₃ and A₇ independently of one another are hydrogen or C₁ -C₁₂alkyl,

A₄, A₅ and A₆ independently of one another are C₂ -C₁₀ alkylene and

T₁, T₂, T₃, T₄, T₅, T₆, T₇ and T₈ independently of one another are agroup of the formula III-2 ##STR21## in which A₈ is hydrogen, C₁ -C₁₂alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl,phenyl, --OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇ -C₉phenylalkyl, C₇ -C₉ phenylalkyl which is substituted on the phenylradical by --OH and/or C₁ -C₁₀ alkyl, or is a group of the formula IV-2##STR22## and A₉ and A₁₀ independently of one another are as defined forA₁ ;

component II-c) is at least one compound of the formula V-2 ##STR23## inwhich T₉, T₁₀ and T₁₁ independently of one another are a group of theformula III-2;

component II-d) is at least one compound of the formula VI-2 ##STR24##in which A₁₁, A₁₃, A₁₄ and A₁₅ independently of one another arehydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅-C₁₂ cycloalkyl, phenyl, --OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl,C₇ -C₉ phenylalkyl, C₇ -C₉ phenylalkyl which is substituted on thephenyl radical by --OH and/or C₁ -C₁₀ alkyl, or are a group of theformula IV-2,

A₁₂ is C₂ -C₁₈ alkylene, C₅ -C₇ cycloalkylene or C₁ -C₄ alkylenedi(C₅-C₇ cycloalkylene), or the radicals A₁₁, A₁₂ and A₁₃, together with thenitrogen atoms to which they are attached, form a 5- to 10-memberedheterocyclic ring, or

A₁₄ and A₁₅, together with the nitrogen atom to which they are attached,form a 5- to 10-membered heterocyclic ring,

b₂ is a number from 2 to 50 and

at least one of the radicals A₁₁, A₁₃, A₁₄ and A₁₅ is a group of theformula IV-2;

component II-e) is at least one compound of the formula VII-2 ##STR25##in which A₁₆ is C₁ -C₁₀ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄alkyl-substituted C₅ -C₁₂ cycloalkyl, phenyl or C₁ -C₁₀alkyl-substituted phenyl,

A₁₇ is C₃ -C₁₀ alkylene,

A₁₈ is as defined for A₁ and

b₃ is a number from 1 to 50;

component II-f) is a product obtainable by reacting a product, obtainedby reaction of a polyamine of the formula VIII-2-a with cyanuricchloride, with a compound of the formula VIII-2-b ##STR26## in which b₄', b₄ " and b₄ '" independently of one another are a number from 2 to12,

A₁₉ is hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, phenyl or C₇ -C₉phenylalkyl and

A₂₀ is as defined for A_(1;)

component II-g) is at least one compound of the formula IX-2 ##STR27##in which A₂₁ and A₂₆ independently of one another are a direct bond or agroup --N(E₁)--CO--E₂ --CO--N(E₃)--,

E₁ and E₃ independently of one another are hydrogen, C₁ -C₈ alkyl, C₅-C₁₂ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formulaIV-2,

E₂ is a direct bond or C₁ -C₄ alkylene,

A₂₂ is as defined for A₁,

A₂₃, A₂₄, A₂₇ and A₂₈ independently of one another are hydrogen, C₁ -C₃₀alkyl, C₅ -C₁₂ cycloalkyl or phenyl,

A₂₅ is hydrogen, C₁ -C₃₀ alkyl, C₅ -C₁₂ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV-2 and

b₅ is a number from 1 to 50;

component II-h) is at least one compound of the formula X-2 ##STR28## inwhich A₂₉ is C₁ -C₂₄ alkyl and

A₃₀ is as defined for A₁ ;

component II-i) is at least one compound of the formula XI-2 ##STR29##in which A₃₁ is as defined for A₁ and

b₆ is a number from 2 to 50;

component II-j) is at least one compound of the formula XII-2 ##STR30##in which A₃₂ and A₃₃ together form C₂ -C₁₄ alkylene,

A₃₄ is hydrogen or a group --G₁ --COO--G₂,

G₁ is C₂ -C₁₄ alkylene and

G₂ is C₁ -C₂₄ alkyl and

A₃₅ is as defined for A₁ ;

component II-k) is at least one compound of the formula XIII-2 ##STR31##in which A₃₆, A₃₇, A₃₈, A₃₉ and A₄₀ independently of one another are adirect bond or C₁ -C₁₀ alkylene,

A₄₁ is as defined for A₁ and

b₇ is a number from 1 to 50;

component II-l) is at least one compound of the formula XIV-2 ##STR32##in which T₁₂, T₁₃ and T₁₄ independently of one another are a group ofthe formula XV-2 ##STR33## in which L is a group of the formula III-2;component II-m) is at least one compound of the formula XVI-2 ##STR34##in which A₄₂ is hydrogen or methyl, A₄₃ is a direct bond or C₁ -C₁₀alkylene and

b₈ is a number from 2 to 50.

Examples of alkyl having up to 30 carbon atoms are methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl,docosyl and triacontyl. One of the preferred definitions of A₁, A₉, A₁₀,A₁₈, A₂₀, A₂₂, A₃₀, A₃₁, A₃₅ and A₄₁ is C₁ -C₄ alkyl, especially methyl.One of the preferred definitions of R₂₃, R₂₇, A₂₃ and A₂₇ is C₁ -C₂₅alkyl, especially C₁₅ -C₂₅ alkyl, for example hexadecyl and C₁₈ -C₂₂alkyl. One of the preferred definitions of R₂₅ and A₂₅ is C₁ -C₂₅ alkyl,especially octadecyl. One of the preferred definitions of R₈, R₁₉, A₈and A₁₉ is C₁ -C₄ alkyl, especially n-butyl.

Examples of C₅ -C₁₂ cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅ -C₈ Cycloalkyl, especially cyclohexyl,is preferred.

In a stabilizer mixture comprising component I-a) and component II-b) orII-m), R₁ is preferably C₁ -C₈ cycloalkyl, especially cyclohexyl.

C₁ -C₄ Alkyl-substituted C₅ -C₁₂ cycloalkyl is for examplemethylcyclohexyl or dimethylcyclohexyl.

--OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl is for examplemethylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C₇ -C₉ phenylalkyl are benzyl and phenylethyl.

C₇ -C₉ Phenylalkyl which is substituted on the phenyl radical by --OHand/or by alkyl having up to 10 carbon atoms is for examplemethylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of C₃ -C₆ alkenyl are allyl, 2-methallyl, butenyl, pentenyl andhexenyl. Allyl is preferred. The carbon atom in position 1 is preferablysaturated.

Examples of alkylene having up to 18 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,octamethylene and decamethylene. R₁₂ and A₁₂ are preferablyhexamethylene, A₄₃ is preferably ethylene, R₃₆, R₃₈, A₃₆ and A₃₈ arepreferably methylene, R₃₉ and A₃₉ are preferably 2,2-dimethylethyleneand R₄₀ and A₄₀ are preferably 1,1-dimethylethylene.

An example of C₄ -C₁₀ alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C₅ -C₇ cycloalkylene is cyclohexylene.

An example of C₁ -C₄ alkylenedi(C₅ -C₇ cycloalkylene) ismethylenedicyclohexylene.

Where the radicals R₁₁, R₁₂, R₁₃ or A₁₁, A₁₂ and A₁₃, together with thenitrogen atoms to which they are attached, form a 5- to 10-memberedheterocyclic ring, this ring is for example ##STR35## A 6-memberedheterocyclic ring is preferred.

Where the radicals R₁₄ and R₁₅ or A₁₄ and A₁₅, together with thenitrogen atom to which they are attached, form a 5- to 10-memberedheterocyclic ring, this ring is for example 1-pyrrolidyl, piperidino,morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl or4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularlypreferred.

One of the preferred definitions of R₂₃, R₂₇, A₂₃ and A₂₇ is phenyl.

Y₂, E₂, R₃₇ and A₃₇ are preferably a direct bond.

One of the preferred definitions of Y₁, Y₃, E₁, E₃, A₁, A₉, A₁₀, A₁₈,A₂₀, A₂₂, A₃₀, A₃₁, A₃₅, A₄₁ and A₄₂ is hydrogen.

n₂ and b₂ are preferably 2-25.

n₃ and b₃ are preferably 1-25, especially 2-20 or 2-10.

n₄ ', n₄ ", n₄ '", b₄ ', b₄ " and b₄ '" are preferably 2-4.

n₅ and b₅ are preferably 1-25, especially 1-20 or 1-10.

n₆ and b₆ are preferably 2-25, especially 2-20 or 2-10.

n₇ and b₇ are preferably 1-25, especially 1-20 or 1-10.

b₈ is preferably 2-25, especially 2-20 or 2-10.

In a stabilizer mixture comprising component I-a) and component II-b) orII-m), R₁ is preferably other than C₁ -C₁₈ alkyl, especially other thanhydrogen and C₁ -C₁₈ alkyl.

In a stabilizer mixture comprising component I-a) and component II-d),if R₁ =C₁ -C₁₈ alkyl, the group --N(A₁₄)A₁₅ is preferably morpholino.

In a stabilizer mixture comprising component I-a) and component II-d),the group --N(A₁₄)A₁₅ is in particular morpholino.

The compounds described as components II-a) to II-m) are essentiallyknown (in some cases commercially available) and can be prepared byknown processes as described, for example, in U.S. Pat. No. 3,640,928,U.S. Pat. No. 4,108,829, U.S. Pat. No. 3,925,376, U.S. Pat. No.4,086,204, U.S. Pat. No. 4,331,586, U.S. Pat. No. 5,051,458, U.S. Pat.No. 4,477,615 and Chemical Abstracts-CAS No. 136 504-96-6, U.S. Pat. No.4,857,595, DD-A-262 439 (Derwent 89-122 983/17, Chemical Abstracts111:58 964u), WO-A-94/12 544 (Derwent 94-177 274/22), U.S. Pat. No.4,356,307, U.S. Pat. No. 4,340,534, U.S. Pat. No. 4,408,051, U.S. Pat.No. 4,689,416, U.S. Pat. No. 4,110,334, U.S. Pat. No. 4,529,760, U.S.Pat. No. 5,182,390 (Chemical Abstracts-CAS No. 144 923-25-1) and U.S.Pat. No. 4,233,412.

Component II-f) can be prepared analogously to known processes, forexample by reacting a polyamine of formula VIII-2-a with cyanuricchloride in a molar ratio of from 1:2 to 1:4 in the presence ofanhydrous lithium carbonate, sodium carbonate or potassium carbonate inan organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene,dioxane or tert-amyl alcohol at a temperature of from -20° C. to +10°C., preferably from -10° C. to +10° C., in particular from 0° C. to +10°C., for from 2 to 8 hours, followed by reaction of the resultant productwith a 2,2,6,6-tetramethyl-4-piperidylamine of the formula VII-2-b. Themolar ratio of 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of theformula VIII-2-a employed is for example from 4:1 to 8:1. The quantityof 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion orin more than one portion at intervals of a few hours.

The ratio of polyamine of the formula VIII-2-a to cyanuric chloride to2,2,6,6-tetramethyl-4-piperidylamine of the formula VIII-2-b ispreferably from 1:3:5 to 1:3:6.

The following example indicates one way of preparing the preferredcomponent II-f).

EXAMPLE

23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) ofN,N'-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrouspotassium carbonate are reacted at 5° C. for 3 hours with stirring in250 ml of 1,2-dichloroethane. The mixture is warmed at room temperaturefor a further 4 hours. 27.2 g (0.128 mol) ofN-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and theresultant mixture is warmed at 60° C. for 2 hours. A further 18 g (0.13mol) of anhydrous potassium carbonate are added and the mixture iswarmed at 60° C. for a further 6 hours. The solvent is removed bydistillation under a slight vacuum (200 mbar) and replaced by xylene.18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture isheated at reflux for 2 hours and, for a further 12 hours, the waterformed during the reaction is removed by azeotropic distillation. Themixture is filtered. The solution is washed with water and dried overNa₂ SO₄. The solvent is evaporated and the residue is dried at 120-130°C. in vacuo (0.1 mbar). Component II-f) is obtained as a colourlessresin.

In general, component II-f) can for example be represented by a compoundof the formula VIII-2-1, VIII-2-2 or VIII-2-3. It can also be in theform of a mixture of these three compounds. ##STR36##

A preferred definition of the formula VIII-2-1 is ##STR37##

A preferred definition of the formula VIII-2-2 is ##STR38##

A preferred definition of the formula VIII-2-3 is ##STR39##

In the above formulae VIII-2-1, VIII-2-2 and VIII-2-3, b₄ is preferablyfrom 1 to 20.

The compounds described as components I-a) to I-l) can be prepared fromthe compounds described as components II-a) to II-l)--the nitrogen atomin the 2,2,6,6-tetramethylpiperid-4-yl group being unsubstituted--inanalogy to known processes, for example as disclosed in U.S. Pat. No.5,204,473, by oxidizing the corresponding 2,2,6,6-tetramethylpiperidinederivative with an appropriate peroxy compound, such as hydrogenperoxide or tert-butyl hydroperoxide, in the presence of a metalcarbonyl or metal oxide catalyst, followed by reduction of the resultingoxyl intermediate to the desired N-hydroxyl derivative, preferably bycatalytic hydrogenation.

After this, the O-alkyl derivatives can be synthesized in various ways.For example, the N-hydroxy derivative can be alkylated with sodiumhydride and halogenated hydrocarbons, such as ethyl iodide. N-Methoxyvariants can be prepared by thermolysis of a chlorobenzene solution ofthe nitroxyl radical and of di-tert-butyl peroxide. The product isformed by a coupling reaction between the nitroxyl radical and themethyl radical which is produced from the β-cleavage of a tert-butoxyradical.

Other N-alkoxy variants can be synthesized by coupling of nitroxylradicals with hydrocarbon radicals, which are formed during the thermaldecomposition of di-tert-butyl peroxide in the presence of hydrocarbonsolvents, such as cyclohexane, toluene and ethylbenzene.

Although these procedures have been described with reference to N-alkoxysubstituents, it will be understood that they can be employed equally toall OR₁ groups.

For example, 1-cycloalkyloxy-2,2,6,6-tetramethylpiperid-4-yl derivativescan be prepared by reacting the corresponding2,2,6,6-tetramethylpiperid-4-yl derivative with tert-butyl hydroperoxidein the presence of MoO₃ and a cycloalkane.

In general, component I-f) can for example also be represented by acompound of the formula VIII-2-1, VIII-2-2 or VIII-2-3 in which theradicals A₂₀ are a group --OR₂₀. It can also be in the form of a mixtureof these three compounds.

The product described as component I-f) is, for example, also obtainableby reacting a product, obtained by reaction of a polyamine of theformula VIII-1-a with cyanuric chloride, with a compound of the formulaVIII-1-b ##STR40## in which n₄ ', n₄ " and n₄ '" independently of oneanother are a number from 2 to 12,

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, phenyl or C₇ -C₉phenylalkyl and

R₂₀ is as defined for R₁.

The reaction can take place, for example, in analogy to the preparationprocess described in U.S. Pat. No. 4,477,615.

With particular preference, component I-a) is ®TINUVIN 123, componentII-a) is ®MARK LA 52 or ®MARK LA 57, component II-b) is ®CHIMASSORB 119,component II-d) is ®CHIMASSORB 944, ®CYASORB UV 3346 or ®DASTIB 1082,component II-e) is ®UVASIL 299 or ®UVASIL 125, component II-f) is®UVASORB HA 88, component II-g) is ®UVINUL 5050 H, ®LICHTSCHUTZSTOFF UV31 or ®LUCHEM HA-B 18, component II-i) is ®HOSTAVIN N 30, componentII-k) is ®MARK LA 63 or ®MARK LA 68 and component II-m) is ®TINUVIN 622.

Other products which can be employed, for example, are as componentII-a) ®Tinuvin 770 or ®DASTIB 845, as component II-h) ®LICHTSCHUTZMITTELS 95 and as component II-j) ®HOSTAVIN N 20 or ®SANDUVOR 3050.

As component I-f) it is preferred to employ ®UVASORB HA 88, in which the2,2,6,6-tetramethylpiperidin-4-yl radicals are replaced by a group ofthe formula VIII-1-c.

If the radical A₃₁ in the compound of the formula XI-2 is hydrogen, thiscompound can be in the form of a mixture with a compound of the formulaXI-2* ##STR41## and can also be employed as such a mixture, as componentII-i), in the stabilizer system of the invention. The ratio ofXI-2:XI-2* is for example from 20:1 to 1:20 or from 1:10 to 10:1.

The definitions of the terminal groups which saturate the free valencesin the compounds of the formulae VI-1, VI-2, VII-1, VII-2, VIII-2-1,VIII-2-2, VIII-2-3, IX-1, IX-2, XI-1, XI-2, XI-2*, XIII-1, XIII-2 andXVI-2 depend on the processes used for their preparation. The terminalgroups can also be modified after the preparation of the compounds.

If the compounds of the formula VI-1 are prepared by reacting a compoundof the formula ##STR42## in which X is for example halogen, especiallychlorine, and R₁₄ and R₁₅ are as defined above, with a compound of theformula ##STR43## in which R₁₁, R₁₂ and R₁₃ are as defined above, thenthe terminal group bonded to the diamino radical is hydrogen or##STR44## and the terminal group bonded to the triazine radical is X or##STR45##

If X is a halogen, it is advantageous to replace it, for example, by--OH or an amino group when the reaction is complete. Examples of aminogroups which may be mentioned are pyrrolidin-1-yl, morpholino, --NH₂,--N(C₁ -C₈ alkyl)₂ and --NR(C₁ C₈ alkyl), in which R is hydrogen or agroup of the formula IV-1.

The comments made above regarding the compounds of the formula VI-1 canbe applied correspondingly to the compounds of the formula VI-2, theradicals R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ corresponding to the respectiveradicals A₁₁, A₁₂, A₁₃, A₁₄ and A₁₅ and the group IV-1corresponding tothe group IV-2.

In the compounds of the formula VII-1 or VII-2 the terminal group bondedto the silicon atom can for example be (R₁₆)₃ Si--O-- or (A₁₆)₃ Si--O--and the terminal group bonded to the oxygen can for example be--Si(R₁₆)₃ or --Si(A₁₆)₃.

The compounds of the formulae VII-1 and VII-2 can also be in the form ofcyclic compounds if n₃ or b₃ is a number from 3 to 10; in other words,the free valences represented in the structural formulae in that caseform a direct bond.

In the compounds of the formulae VIII-2-1, VIII-2-2 and VII-2-3 theterminal group bonded to the triazine radical is for example Cl or agroup ##STR46## and the terminal group bonded to the amino radical isfor example hydrogen or a group ##STR47##

In the compounds of the formula IX-1, the terminal group bonded to the2,5-dioxopyrrolidine ring is for example hydrogen and the terminal groupbonded to the radical --C(R₂₇)(R₂₈)-- is for example ##STR48##

In the compounds of the formula IX-2 the terminal group bonded to the2,5-dioxopyrrolidine ring is for example hydrogen and the terminal groupbonded to the radical --C(A₂₇)(A₂₈)-- is for example ##STR49##

In the compounds of the formula XI-1 and XI-2 the terminal group bondedto the dimethylene radical can for example be --OH and the terminalgroup bonded to the oxygen can for example be hydrogen. The terminalgroups can also be polyether radicals.

In the compounds of the formula XI-2*, the terminal group bonded to thenitrogen can for example be hydrogen and the terminal group bonded tothe 2-hydroxypropylene radical can for example be a group ##STR50##

In the compounds of the formula XIII-1, the terminal group bonded to thecarbonyl radical is for example ##STR51## and the terminal group bondedto the oxygen radical is for example ##STR52##

In the compounds of the formula XIII-2 the terminal group bonded to thecarbonyl radical is for example ##STR53## and the terminal group bondedto the oxygen radical is for example ##STR54##

Where the preparation of the compounds of the formula XVI-2 takes place,for example, by reacting a compound of the formula ##STR55## in whichA₄₂ is as defined above, with a dicarboxylic diester of the formulaQ--OOC--A₄₃ --COO--Q, in which Q is for example methyl, ethyl or propyland A₄₃ is as defined above, the terminal group bonded to the2,2,6,6-tetramethyl-4-oxypiperid-1-yl radical is hydrogen or --CO--A₄₃--COO--Q and the terminal group bonded to the diacyl radical is --O--Qor ##STR56##

A preferred stabilizer mixture is one in which R₁, R₉, R₁₀, R₁₈, R₂₀,R₂₂, R₃₀, R₃₁, R₃₅ and R₄₁ independently of one another are C₁ -C₁₂alkyl, C₅ -C₈ cycloalkyl or methyl-substituted C₅ -C₈ cycloalkyl.

Preference is likewise given to a stabilizer mixture in which R₁, R₉,R₁₀, R₁₈, R₂₀, R₂₂, R₃₀, R₃₁, R₃₅ and R₄₁ independently of one anotherare methyl, octyl or cyclohexyl.

Also of interest is a stabilizer mixture in which A₁, A₉, A₁₀, A₁₈, A₂₀,A₂₂, A₃₀, A₃₁, A₃₅ and A₄₁ independently of one another are hydrogen ormethyl.

A preferred embodiment corresponds also to a stabilizer mixturecomprising a component I-a), I-b), I-c), I-d), I-e), I-f), I-g), I-h),I-i), I-j), I-k) or I-l) and a component II-a), II-b), II-d), II-e),II-f), II-g), II-i), II-k) or II-m).

The following stabilizer mixtures may be mentioned as examples:

1. stabilizer mixture comprising a component I-a) and a component II-b),II-d) or II-m),

2. stabilizer mixture comprising a component I-b) and a component II-b),II-d) or II-m) and

3. stabilizer mixture comprising a component I-c) and a component II-b),II-d) or II-m).

Also preferred is a stabilizer mixture

in which n₁ is 1, 2 or 4,

if n₁ is 1, R₂ is C₁₀ -C₂₀ alkyl,

if n₁ is 2, R₂ iS C₆ -C₁₀ alkylene and

if n₁ is 4, R₂ is butanetetrayl;

R₃ and R₇ independently of one another are hydrogen or C₁ -C₄ alkyl,

R₄, R₅ and R₆ independently of one another are C₂ -C₆ alkylene,

R₈ is hydrogen, C₁ -C₆ alkyl, C₅ -C₈ cycloalkyl, methyl-substituted C₅-C₈ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formulaIV-1;

R₁₁, R₁₃, R₁₄ and R₁₅ independently of one another are hydrogen, C₁ -C₈alkyl, C₅ -C₈ cycloalkyl, methyl-substituted C₅ -C₈ cycloalkyl, phenyl,C₇ -C₉ phenylalkyl or a group of the formula IV-1, or

the radicals R₁₄ and R₁₅, together with the nitrogen atom to which theyare attached, form a 6-membered heterocyclic ring,

R₁₂ is C₂ -C₁₀ alkylene and

n₂ is a number from 2 to 25;

R₁₆ is C₁ -C₄ alkyl, C₅ -C₈ cycloalkyl or phenyl,

R₁₇ is C₃ -C₆ alkylene and

n₃ is a number from 1 to 25;

n₄ ', n₄ " and n₄ '" independently of one another are a number from 2 to4 and

R₁₉ is C₁ -C₄ alkyl;

R₂₁ and R₂₆ independently of one another are a direct bond or a group--N(Y₁)--CO--Y₂ --CO--N(Y₃)--,

Y₁ and Y₃ independently of one another are hydrogen or C₁ -C₄ alkyl,

Y₂ is a direct bond,

R₂₃ and R₂₇ are C₁ -C₂₅ alkyl or phenyl,

R₂₄ and R₂₈ are hydrogen or C₁ -C₄ alkyl,

R₂₅ is C₁ -C₂₅ alkyl or a group of the formula IV-1 and

n₅ is a number from 1 to 25;

R₂₉ is C₈ -C₁₅ alkyl;

n₆ is a number from 2 to 25;

R₃₂ and R₃₃ together form C₈ -C₁₄ alkylene,

R₃₄ is hydrogen or a group --Z₁ --COO--Z₂,

Z₁ is C₂ -C₆ alkylene and

Z₂ is C₈ -C₁₅ alkyl;

R₃₆, R₃₈, R₃₉ and R₄₀ independently of one another are C₁ -C₄ alkylene,

R₃₇ is a direct bond and

n₇ is a number from 1 to 25.

Particular preference is given to a stabilizer mixture in which

component I-a) is at least one compound of the formula I-1-a-1, I-1-a-2or I-1-a-3 ##STR57## in which R₁ is methyl, octyl or cyclohexyl;component I-b) is at least one compound of the formula II-1-b ##STR58##in which R₉ is as defined for R₁ ; component I-c) is at least onecompound of the formula V-1-c ##STR59## in which R₉ is as defined above;component I-d) is at least one compound of the formula VI-1-d-1,VI-1-d-2 or VI-1-d-3 ##STR60## in which R₁₀ is as defined for R₁ and n₂is a number from 2 to 25;

component I-e) is at least one compound of the formula VII-1-e ##STR61##in which R₁₈ is as defined for R₁ and n₃ is a number from 1 to 25;

component I-f) is a product obtainable by

a) reacting a product, obtained by reaction of a polyamine of theformula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

with cyanuric chloride, with a compound of the formula ##STR62## b)further reacting the 2,2,6,6-tetramethylpiperid-4-yl groups which arepresent in the molecule to give groups of the formula VIII-1-c;

component 1-g) is at least one compound of the formula IX-1-g-1,IX-1-g-2 or IX-1-g-3 ##STR63## in which R₁₀ and R₂₂ are as defined forR₁ and n₅ is a number from 1 to 25;

component 1-h) is at least one compound of the formula X-1-h ##STR64##in which R₃₀ is as defined for R₁ ; component I-i) is at least onecompound of the formula (XI-1) in which R₃₁ is as defined for R₁ and n₆is a number from 2 to 25;

component I-j) is at least one compound of the formula XII-1-j-1 orXII-1-j-2 ##STR65## in which R₃₅ is as defined for R₁ ; component I-k)is at least one compound of the formula XIII-1-k ##STR66## in which R₄₁is as defined for R₁ and n₇ is a number from 1 to 25;

component I-l) is at least one compound of the formula XIV-1-l ##STR67##in which R₉ is as defined for R₁.

Preference is furthermore given to a stabilizer mixture

in which b₁ is 1, 2 or 4,

if b₁ is 1, A₂ is C₁₀ -C₂₀ alkyl,

if b₁ is 2, A₂ is C₆ -C₁₀ alkylene and

if b₁ is 4, A₂ is butanetetrayl;

A₃ and A₇ independently of one another are hydrogen or C₁ -C₄ alkyl,

A₄, A₅ and A₆ independently of one another are C₂ -C₆ alkylene,

A₈ is hydrogen, C₁ -C₆ alkyl, C₅ -C₈ cycloalkyl, methyl-substituted C₅-C₈ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formulaIV-2;

A₁₁, A₁₃, A₁₄ and A₁₅ independently of one another are hydrogen, C₁ -C₈alkyl, C₅ -C₈ cycloalkyl, methyl-substituted C₅ -C₈ cycloalkyl, phenyl,C₇ -C₉ phenylalkyl or a group of the formula IV-2, or

the radicals A₁₄ and A₁₅, together with the nitrogen atom to which theyare attached, form a 6-membered heterocyclic ring,

A₁₂ is C₂ -C₁₀ alkylene and

b₂ is a number from 2 to 25;

A₁₆ is C₁ -C₄ alkyl, C₅ -C₈ cycloalkyl or phenyl,

A₁₇ is C₃ -C₆ alkylene and

b₃ is a number from 1 to 25;

b₄ ', b₄ " and b₄ '" independently of one another are a number from 2 to4 and

A₁₉ is C₁ -C₄ alkyl;

A₂₁ and A₂₆ independently of one another are a direct bond or a group--N(E₁)--CO--E₂ --CO--N(E₃)--,

E₁ and E₃ independently of one another are hydrogen or C₁ -C₄ alkyl,

E₂ is a direct bond,

A₂₃ and A₂₇ are C₁ -C₂₅ alkyl or phenyl,

A₂₄ and A₂₈ are hydrogen or C₁ -C₄ alkyl,

A₂₅ is C₁ -C₂₅ alkyl or a group of the formula IV-2 and

b₅ is a number from 1 to 25;

A₂₉ is C₈ -C₁₅ alkyl;

b₆ is a number from 2 to 25;

A₃₂ and A₃₃ together form C₈ -C₁₄ alkylene,

A₃₄ is hydrogen or a group --G₁ --COO--G₂,

G₁ is C₂ -C₆ alkylene and

G₂ is C₈ -C₁₅ alkyl;

A₃₆, A₃₈, A₃₉ and A₄₀ independently of one another are C₁ -C₄ akylene,

A₃₇ is a direct bond and

b₇ is a number from 1 to 25.

Particular preference is given to a stabilizer mixture in which

component II-a) is at least one compound of the formula I-2-a-3##STR68## in which A₁ is hydrogen or methyl; component II-b) is at leastone compound of the formula II-2-b ##STR69## in which A₉ is as definedfor A₁ ; component II-d) is at least one compound of the formulaVI-2-d-1, VI-2-d-2 or VI-2-d-3 ##STR70## in which A₁₀ is as defined forA₁ and b₂ is a number from 2 to 25;

component II-e) is at least one compound of the formula VI-2-e ##STR71##in which A₁₈ is as defined for A₁ and b₃ is a number from 1 to 25;

component II-f) is a product obtainable by reacting a product, obtainedby reaction of a polyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

with cyanuric chloride, with a compound of the formula ##STR72## inwhich A₂₀ is as defined for A₁ ; component II-g) is at least onecompound of the formula IX-2-g-1, IX-2-g-2 or IX-2-g-3 ##STR73## inwhich A₁₀ and A₂₂ are as defined for A₁ and b₅ is a number from 1 to 25;

component II-i) is at least one compound of the formula XI-2 in whichA₃₁ is as defined for A₁ and b₆ is a number from 2 to 25;

component II-k) is at least one compound of the formula XIII-2-k##STR74## in which A₄₁ is as defined for A₁ and b₇ is a number from 1 to25;

component II-m) is at least one compound of the formula XVI-2-m##STR75## in which b₈ is a number from 2 to 25.

Particular interest attaches to the following stabilizer systems:

a) stabilizer mixture comprising at least one compound of the formulaI-1-a-1 in which R₁ is cyclohexyl, and at least one compound of theformula XVI-2-m,

b) stabilizer mixture comprising at least one compound of the formulaI-1-a-1 in which R₁ is cyclohexyl, and at least one compound of theformula VI-2-d-1 in which A₁₀ is hydrogen,

c) stabilizer mixture comprising at least one compound of the formulaI-1-a-1 in which R₁ is cyclohexyl, and at least one compound of theformula II-2-b in which A₉ is methyl,

d) stabilizer mixture comprising at least one compound of the formulaII-1-b in which R₉ is cyclohexyl, and at least one compound of theformula XVI-2-m,

e) stabilizer mixture comprising at least one compound of the formulaII-1-b in which R₉ is cyclohexyl, and at least one compound of theformula VI-2-d-1 in which A₁₀ is hydrogen,

f) stabilizer mixture comprising at least one compound of the formulaII-1-b in which R₉ is cyclohexyl, and at least one compound of theformula II-2-b in which A₉ is methyl,

g) stabilizer mixture comprising at least one compound of the formulaV-1-c in which R₉ is cyclohexyl, and at least one compound of theformula XVI-2-m,

h) stabilizer mixture comprising at least one compound of the formulaV-1-c in which R₉ is cyclohexyl, and at least one compound of theformula VI-2-d-1 in which A₁₀ is hydrogen,

i) stabilizer mixture comprising at least one compound of the formulaV-1-c in which R₉ is cyclohexyl, and at least one compound of theformula II-2-b in which A₉ is methyl,

j) stabilizer mixture comprising at least one compound of the formulaV-1-c in which R₉ is methyl, and at least one compound of the formulaXVI-2-m,

k) stabilizer mixture comprising at least one compound of the formulaV-1-c in which R₉ is methyl, and at least one compound of the formulaVI-2-d-1 in which A₁₀ is hydrogen,

l) stabilizer mixture comprising at least one compound of the formulaV-1-c in which R₉ is methyl, and at least one compound of the formulaII-2-b in which A₉ is methyl,

m) stabilizer mixture comprising at least one compound of the formulaI-1-a-1 in which R₁ is octyl, and at least one compound of the formulaVI-2-d-2 in which A₁₀ is hydrogen,

n) stabilizer mixture comprising at least one compound of the formulaI-1-a-1 in which R₁ is octyl, and a product obtainable by reacting aproduct, obtained by reaction of a polyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

with cyanuric chloride, with a compound of the formula ##STR76##

In the abovementioned stabilizer systems, the two components areparticularly preferably in a weight ratio of from 1:4 to 1:1.

The novel stabilizer mixture is suitable for stabilizing organicmaterials against thermal, oxidative or light-induced degradation.Examples of such materials are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPB) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPB) and mixtures thereof with low densitypolyethylene (LDPB), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbomene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLEDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or a-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; andalso block copolymers of the aforementioned polyamides with polyolefins,olefin copolymers, ionomers or chemically bonded or grafted elastomers;or with polyethers, e.g. with polyethylene glycol, polypropylene glycolor polytetramethylene glycol; as well as polyamides or copolyamidesmodified with EPDM or ABS; and polyamides condensed during processing(RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethyloicyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/forrnaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

The invention therefore additionally relates to a composition comprisingan organic material which is sensitive to oxidative, thermal orlight-induced degradation and a novel stabilizer mixture.

The organic material is preferably a synthetic polymer, in particularfrom one of the above groups. Polyolefins are preferred andpolyethylene, polypropylene and copolymers thereof are particularlypreferred.

The components of the novel stabilizer system can be added to thematerial to be stabilized either individually or mixed with one another.In this context, component I-a), I-b), I-c), I-d), I-e), I-f), I-g),I-h), I-i), I-j), I-k) or I-l) can be employed in a quantity of from0.01 to 2.5%, preferably from 0.05 to 0.5%, and component II-a), II-b),II-c), II-d), II-e), II-f), II-g), II-h), II-i), II-j), II-k), II-l) orII-m) can be employed in a quantity of from 0.01 to 4.99%, preferablyfrom 0.05 to 1.5%, with the proviso that the total quantity of componentI-a), I-b), I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l)and component II-a), II-b), II-c), II-d), II-e), II-f), II-g), II-h),II-i), II-j), II-k), II-l) or II-m) is from 0.02 to 5%, based on theoverall weight of the material to be stabilized.

The total quantity of component I-a), I-b), I-c), I-d), I-e), I-f),I-g), I-h), I-i), I-j), I-k) or I-l) and component II-a), II-b), II-c),II-d), II-e), II-f), II-g), II-h), II-i), II-j), II-k), II-l) or II-m)is preferably from 0.05 to 3%, in particular from 0.05 to 2% or from0.05 to 1%, based on the overall weight of the material to bestabilized.

The weight ratio of component I-a), I-b), I-c), I-d), I-e), I-f), I-g),I-h), I-i), I-j), I-k) or I-l) to component II-a), II-b), II-c), II-d),II-e), II-f), II-g), II-h), II-i), II-j), II-k), II-l) or II-m) ispreferably from 20:1 to 1:20, in particular from 10:1 to 1:10, forexample from 1:5 to 5:1 or from 1:4 to 1:1.

The novel stabilizer mixture or the individual components can beincorporated into the organic material by known methods, for examplebefore or during shaping or by applying the dissolved or dispersedcompounds to the organic material, if desired with subsequentevaporation of the solvent. The individual components of the novelstabilizer mixture can be added to the materials to be stabilized in theform of a powder, as granules or as a masterbatch, which contains thesecomponents in, for example, a concentration of from 2.5 to 25% byweight.

If desired, before incorporation, the components of the novel stabilizersystem can be mixed with one another in a melt (melt blending).

The novel stabilizer system or its components can be added before orduring polymerization or prior to crosslinking.

The materials stabilized in this way can be employed in a wide varietyof forms, for example as films, fibres, tapes, moulding compositions orprofiles or as binders for coatings, adhesives or putties.

The stabilized organic materials of the invention can additionallycomprise various conventional additives, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. 1Hydroguinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol),4,4'-thiobis(6-tert-butyl-2-methylphenol),4,4'-thiobis-(3,6-di-sec-amylphenol),4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol),2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2'-methylenebis(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)alonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tiazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N'-di-isopropyl-p-phenylenediamine,N,N'-di-sec-butyl-p-phenylenediamine,N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N'-bis(1-methylheptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,N,N'-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N'-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,N-cyclohexyl-N'-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)-diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, Bis[4-(1',3'-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octylphenothiazines, N-allylphenothiazin,N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,mixture of2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R--CH₂ CH₂ --COO(CH₂)₃ .paren close-st.₂,where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxyand 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbarnate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentmethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dion,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide,N,N'-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide,N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N'-diacetyladipol dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide,N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers ("ionomers").

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4 316 611, DE-A-4316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The weight ratio of novel stabilizer mixture to the conventionaladditives can for example be from 1:0.5 to 1:5.

The invention furthermore relates to the use of the novel stabilizermixture for stabilizing organic material against oxidative, thermal orlight-induced degradation.

The organic materials stabilized by means of the novel stabilizer systemare distinguished not only by significantly improved light stability butalso, in some cases, by improved thermal stability.

The compounds of the formulae IX-1-g-1, XI-1, XII-1, XIII-1 and XIV-1and the product defined as component I-f) are novel and are likewise asubject of the present invention.

The present invention also relates to:

1) Compounds of the formula D ##STR77## in which R₁₁ and R₁₃independently of one another are hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl, phenyl, --OH--and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇ -C₉ phenylalkyl, C₇ -C₉phenylalkyl which is substituted on the phenyl radical by --OH and/or C₁-C₁₀ alkyl, or are a group of the formula IV-1 ##STR78## in which R₁₀ ishydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or C₁ C₄ alkyl-substitutedC₅ -C₁₂ cycloalkyl,

R₁₂ is C₂ -C₁₈ alkylene, C₅ -C₇ cycloalkylene or C₁ -C₄ alkylenedi(C₅-C₇ cycloalkylene), or

the radicals R₁₁, R₁₂ and R₁₃, together with the nitrogen atoms to whichthey are attached, form a 5- to 10-membered heterocyclic ring,

the radicals R₁₄ and R₁₅, together with the nitrogen atom to which theyare attached, form a 5- to 10-membered heterocyclic ring or a group--NH(C₅ -C₁₂ cycloalkyl),

n₂ is a number from 2 to 50 and

at least one of the radicals R₁₁ and R₁₃ is a group of the formula IV-1.

R₁₁ and R₁₃ are preferably a group of the formula IV-1.

R₁₂ is preferably C₂ -C₁₀ alkylene, especially hexamethylene.

The radicals R₁₄ and R₁₅, together with the nitrogen atom to which theyare attached, preferably form morpholino or a group --NH(cyclohexyl).

2) Compounds of the formula G-1 ##STR79## in which R₂₂ is hydrogen, C₁-C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or C₁ -C₄ alkyl-substituted C₅ -C₁₂cycloalkyl,

R₂₄ and R₂₈ independently of one another are hydrogen, C₁ -C₃₀ alkyl, C₅-C₁₂ cycloalkyl or phenyl,

R₂₅ is hydrogen, C₁ -C₃₀ alyl, C₅ -C₁₂ cycloalkyl, phenyl, C₇ -C₉phenylakyl or a group of the formula IV-1 ##STR80## in which R₁₀ is asdefined for R₂₂ and n₅ is a number from 1 to 50.

R₂₄ and R₂₈ are preferably C₁ -C₄ alkyl, especially methyl.

R₂₅ is preferably C₁ -C₂₅ alkyl.

3) Compounds of the formula G-2 ##STR81## in which R₂₁ and R₂₆ are agroup --N(Y₁)--CO--Y₂ --CO--N(Y₃)--,

Y₁ and Y₃ independently of one another are hydrogen, C₁ -C₈ alkyl, C₅-C₁₂ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formulaIV-1 ##STR82## in which R₁₀ is hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl or C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl,

Y₂ is a direct bond or C₁ -C₄ alkylene,

R₂₂ is as defined for R₁₀,

R₂₃, R₂₄, R₂₇ and R₂₈ independently of one another are hydrogen, C₁ -C₃₀alkyl, C₅ -C₁₂ cycloalkyl or phenyl,

R₂₅ is hydrogen, C₁ -C₃₀ alkyl, C₅ -C₁₂ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV-1 and

n₅ is a number from 1 to 50.

Y₁ and Y₃ are preferably hydrogen.

R₂₅ is preferably a group of the formula IV-1.

The explanations and expressions of preference made with regard to thenovel stabilizer mixtures, in respect of the variable radicals and theterminal groups, are to be applied correspondingly to the novelcompounds.

The examples which follow illustrate the invention in greater detail.All percentages are by weight, unless stated otherwise.

Example A

Preparation of the compound of the formula ##STR83##

A solution of 23.6 g (0.098 mol) of4-n-butylamino-1-methoxy-2,2,6,6-tetramethylpiperdine in 25 ml of xyleneis added dropwise to a solution of 4.09 (0.0217 mol) of cyanuricchloride in 50 ml of xylene and 6.2 g (0.098 mol) of pulverulent KOH.The reaction mixture is heated at reflux for 23 hours. The solids arethen removed by filtration and the filtrate is concentrated underreduced pressure. The crude product obtained is purified bycrystallization (ethanol) to give 14.3 g (82% of theory) of the productindicated above as a white powder. The melting point is 151-153° C.

Elemental analysis for C₄₅ H₈₇ N₉ O₃ ; Calculated: C, 67.4; H, 10.9; N,15.7; Found: C, 67.4; H, 11.3; N, 15.7

Example B

Preparation of the compound of the formula ##STR84## 0.5 g of MoO₃ isadded to a solution of 24.0 g of the compound of the formula ##STR85##in 200 ml of cyclohexane. The solution is heated at reflux and 20 ml oftert-butyl hydroperoxide (90%) are added over the course of 15 minutes.After the reaction mixture has been heated at reflux for 12 hours, thecatalyst is removed by filtration and a further 0.5 g of MoO₃ is addedto the filtrate, followed by 20 ml of 90% tert-butyl hydroperoxide.After heating at reflux for a further 12 hours, the red colour hasdisappeared. The reaction mixture is washed with 5% aqueous Na₂ SO₃solution until excess hydroperoxide is no longer present. The reactionsolution is washed with water and saline solution, dried over MgSO₄ andevaporated. 15 g of the compound indicated above are obtained as a clearviscous resin without crystals. The NMR and MS data agree with thestructure indicated.

Example C

Preparation of the compound of the formula ##STR86##

This is prepared in analogy to the process described in Example B, using31.87 g of the compound of the formula ##STR87## 1.0 g Of MoO₃ and 40 mlof 90% tert-butyl hydroperoxide in 600 ml of cyclohexane. 22.2 g of thecompound indicated above are obtained as a white, vitreous solid. Themelting point is 135° C. The NMR and MS data agree with the structureindicated.

Example D

Preparation of the compound of the formula ##STR88##

This is prepared in analogy to the process described in Example B, using25.1 g of the compound of the formula ##STR89## 2.0 g of MoO₃ and 25 mlof 90% tert-butyl hydroperoxide in 500 ml of cyclohexane. 36.5 g of thecompound indicated above are obtained as a pale yellow vitreous solid.The melting point is 105-125° C. The NMR and MS data agree with thestructure indicated.

Example E

Preparation is carried out in analogy to the process described inExample B, using 25.8 g of ®UVASOR HA 88 [a compound obtainable byreacting a product, obtained by reaction of a polyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

with cyanuric chloride, with a compound of the formula ##STR90## 2.0 gof MoO₃ and 40 ml of 70% tert-butyl hydroperoxide in 500 ml ofcyclohexane. 47.7 g of a corresponding compound are obtained whichcomprises 1-cyclohexyloxy-2,2,6,6-tetramethylpiperid-4-yl groups insteadof 2,2,6,6-tetramethylpiperid-4-yl groups. The compound is a pale yellowresin with some white crystals. The melting point is 135-145° C.Sintering is at 112° C. The NMR and MS data agree with the structureindicated.

Example F

Preparation of the compound of the formula ##STR91## 11.0 g (14.5 mmolbased on the repetitive unit) of the compound of the formula ##STR92##are dissolved in 200 ml of cyclohexane. 0.1 g of MoO₃ is added and themixture is heated at reflux. 10 g (77.5 mmol) of a 70% (% weight/weight)aqueous tert-butyl hydroperoxide solution are added dropwise slowly at80° C. the water/tert-butanol mixture which forms during the reaction isremoved by azeotropic distillation. The mixture is then heated at refluxfor 14 hours, cooled to 20-30° C., added to carbon powder and filtered.The solution is washed twice with 10% (% weight/weight) aqueous Na₂ SO₃and with water. The organic phase is dried over Na₂ SO₄, filtered andevaporated at 80° C./24 mbar. The residue obtained is a white powder andhas a melting point of 104-108° C. Analysis by NMR (¹ H, ¹³ C) agreeswith the structure indicated above.

Example G

Preparation of the compound of the formula ##STR93##

This is prepared in analogy to the process described in Example F. 11 g(10.3 mmol based on the repetitive unit) of the compound of the formula##STR94## are reacted with 10 g of a 10% (% weight/weight) tert-butylhydroperoxide solution in cyclohexane in the presence of 0.1 g of MoO₃.Following evaporation, a white sold with a melting point of 135-139° C.is obtained. Analysis by NMR (¹ H, ¹³ C) agrees with the structureindicated above.

Example H

Preparation of the compound of the formula ##STR95##

This is prepared in analogy to the process described in Example F. 19 g(30.8 mmol based on the repetitive unit) of the compound of the formula##STR96## are reacted with 6.6 g of a 70% (% weight/weight) aqueoustert-butyl hydroperoxide solution in cyclohexane in the presence of 0.5g of MoO₃. Following evaporation, a yellow solid with a melting point of80-87° C. is obtained. Analysis by NMR (¹ H, ¹³ C) agrees with thestructure indicated above.

Example I

Preparation of the compound of the formula ##STR97##

This is prepared in analogy to the process described in Example F. 30 g(39.2 mmol based on the repetitive unit) of the compound of the formula##STR98## are reacted with 15.2 g of a 70% (% weight/weight) aqueoustert-butyl hydroperoxide solution in cyclohexane in the presence of 0.8g of MoO₃. Following evaporation, a yellow solid with a melting point of72-77° C. is obtained. Analysis by NMR (¹ H, ¹³ C) agrees with thestructure indicated above.

The light stabilizers used in Examples 1 to 3:

(The mean degree of polymerization is indicated in each case.)

Light stabilizer 1-a-1 (U.S. Pat. No. 5,204,473, Example 58): ##STR99##Light stabilizer 1-a-2 (U.S. Pat. No. 5,204,473, Example 4): ##STR100##Light stabilizer 1-b-1 (U.S. Pat. No. 5,204,473, Example 62): ##STR101##Light stabilizer 1-c-1 (Example A): ##STR102## Light stabilizer 1-c-2(U.S. Pat. No. 5,204,473, Example 63): ##STR103## Light stabilizer 1-d-1(Example D): ##STR104## Light stabilizer 1-d-2 (Example C): ##STR105##Light stabilizer 1-d-3 (Example I): ##STR106## Light stabilizer 1-e-1(Example B): ##STR107## Light stabilizer 1-f-1 (Example E):

®UVASORB HA 88 comprising1-cyclohexyloxy-2,2,6,6-tetramethylpiperid-4-yl groups instead of2,2,6,6-tetramethylpiperid-4-yl groups.

Light stabilizer 1-g-1 (Example H): ##STR108## Light stabilizer 1-g-2(Example G): ##STR109## Light stabilizer 1-k-1 (Example F): ##STR110##Light stabilizer 2-a-3: ##STR111## Light stabilizer 2-a-4: ##STR112##Light stabilizer 2-b-1: ##STR113## Light stabilizer 2-d-1: ##STR114##Light stabilizer 2-d-2: ##STR115## Light stabilizer 2-d-3: ##STR116##Light stabilizer 2-e-1: ##STR117## Light stabilizer 2-f-1:

Compound obtainable by reacting a product, obtained by reaction of apolyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

with cyanuric chloride, with a compound of the formula ##STR118## Lightstabilizer 2-g-1: ##STR119## Light stabilizer 2-g-2: ##STR120## Lightstabilizer 2-i-1:

Mixture of the compounds ##STR121## in a ratio of about 4:1. Lightstabilizer 2-k-1: ##STR122## Light stabilizer 2-k-2: ##STR123## Lightstabilizer 2-m-1: ##STR124##

Example 1

Light stabilization in low-density polyethylene films.

100 parts of low-density (density=0.918 g/cm³) polyethylene powder arehomogenized with 0.03 part of octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and with the proportionof light stabilizers indicated in Table 1 in a Brabender plastograph at180° C. for 10 minutes. The composition thus obtained is removed fromthe compounder as rapidly as possible and compressed in a press to givea sheet with a thickness of 2-3 mm. A piece of the resultant greenpressure moulding is cut out and pressed between two high-gloss hardaluminium foils for 6 minutes at 170° C. under 12 tonnes using alaboratory press to give a film with a thickness of 0.2 mm, which isimmediately quenched in cold water. Sections each measuring 55×9 mm² arepunched out of this film and stored under SO₂ gas in a desciccator for24 hours. The films are then exposed in an SEPAP 12.24. These testspecimens are removed from the exposure apparatus at regular intervalsand tested for their carbonyl content in an FTIR spectrometer.

A measure for the protective action is the time (T₀.2 measured) neededto reach a carbonyl extinction of 0.2. The results are summarized inTable 1.

The synergistic effect is determined by a comparison of the calculatedT₀.2 value with the measured T₀.2 value. The T₀.2 values are calculatedon the basis of the additivity law (B. Ranby and J. F. Rabek,Photodegradation, Photo-oxidation and Photo stabilization of Polymers,Principles and Applications, a Wiley-Interscience Publication, 1975,pages 418-422) according to the following equation: ##EQU1##

There is a synergistic effect for the mixture in question, when T₀.2measured >T₀.2 calculated.

                  TABLE 1                                                         ______________________________________                                        Light stabilization in low-density polyethylene films.                                            T.sub.0.2 measured                                                                      T.sub.0.2 calculated                              Light stabilizer in hours in hours                                          ______________________________________                                        none (control)   55                                                             0.15% (1-b-1) 1730                                                            0.15% (2-d-1)  615                                                            0.075% (1-b-1) 1600 1173                                                      and 0.075% (2-d-1)                                                          ______________________________________                                    

Example 2

Light stabilization in polypropylene block copolymer films.

100 parts of polypropylene block copolymer powder are homogenized with0.05 part of pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.10 part oftris(2,4-di-tert-butylphenyl) phosphite, 0.1 part of Ca stearate andwith the light stabilizers indicated in Table 2 in a Brabenderplastograph at 200° C. for 10 minutes. The composition thus obtained isremoved from the compounder as rapidly as possible and compressed in atoggle press to give a sheet with a thickness of 2-3 mm. A piece of theresultant green press-moulding is cut out and pressed between twohigh-gloss hard aluminium foils for 6 minutes at 260° C. using alaboratory hydraulic press to give a film with a thickness of 0.5 mm,which is immediately cooled in a water-cooled press. Sections eachmeasuring 60 mm×25 mm are then punched out of this 0.5 mm film and areexposed in a WEATHER-OMETIER Ci 65 (black panel temperature 63±2° C., noirrigation). These test specimens are removed from the exposureapparatus at regular intervals and tested for their carbonyl content inan IR spectrometer. The increase in the carbonyl extinction on exposureis a measure of the photo oxidative degradation of the polymer and isknown from experience to be associated with a deterioration in themechanical properties.

The time (T₀.2 measured) needed to reach a carbonyl extinction of 0.2 isshown in Table 2.

The synergistic effect is determined by a comparison of the calculatedT₀.2 value with the measured T₀.2 value as shown in Example 1.

                  TABLE 2                                                         ______________________________________                                        Light stabilization action in polypropylene block copolymer films.                                   T.sub.0.2 measured                                                                      T.sub.0.2 calculaLed                           Light stabilizer in hours in hours                                          ______________________________________                                        None                120                                                         0.1% of compound 2-m-1 1250                                                   0.1% of compound 2-d-1  870                                                   0.1% of compound 2-b-1 1480                                                   0.1% of compound 2-d-2 1290                                                   0.1% of compound 2-f-1 1150                                                   0.1% of compound 2-i-1 1040                                                   0.1% of compound 2-g-1  515                                                   0.1% of compound 2-g-2  340                                                   0.1% of compound 2-k-2  865                                                   0.1% of compound 2-k-1  675                                                   0.1% of compound 2-e-1 1730                                                   0.1% of compound 2-a-4 1370                                                   0.1% of compound 2-a-3 1320                                                   0.1% of compound 1-k-1  755                                                   0.1% of compound 1-g-2  300                                                   0.1% of compound 1-a-1  955                                                   0.1% of compound 1-b-1  680                                                   0.1% of compound 1-c-2 1210                                                   0.1% of compound 1-e-1 1300                                                   0.1% of compound 1-d-2  265                                                   0.1% of compound 1-d-1  440                                                   0.1% of compound 1-f-1  600                                                   0.05% of compound 1-e-1 and 1520 1275                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-e-1 and 1740 1085                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-e-1 and 1750 1390                                         0.05% of compound 2-b-1                                                       0.05% of compound 1-e-1 and 1550 1295                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-e-1 and 1710 1225                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-e-1 and 1500 1170                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-e-1 and 1220  907                                         0.05% of compound 2-g-1                                                       0.05% of compound 1-e-1 and  900  820                                         0.05% of compound 2-g-2                                                       0.05% of compound 1-e-1 and 1330 1082                                         0.05% of compound 2-k-2                                                       0.05% of compound 1-e-1 and 1330  987                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-e-1 and 1720 1515                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-e-1 and 1760 1335                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-e-1 and 1810 1310                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-d-1 and 1015  845                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-d-1 and  810  655                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-d-1 and 1095  960                                         0.05% of compound 2-b-1                                                       0.05% of compound 1-d-1 and  960  865                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-d-1 and  875  795                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-d-1 and  915  740                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-d-1 and  625  477                                         0.05% of compound 2-g-1                                                       0.05% of compound 1-d-1 and  467  390                                         0.05% of compound 2-g-2                                                       0.05% of compound 1-d-1 and  730  652                                         0.05% of compound 2-k-2                                                       0.05% of compound 1-d-1 and  635  557                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-d-1 and 1430 1085                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-d-1 and 1020  905                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-d-1 and  980  880                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-c-2 and 1430 1230                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-c-2 and 1320 1040                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-c-2 and 1550 1345                                         0.05% of compound 2-b-1                                                       0.05% of compound 1-c-2 and 1410 1250                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-c-2 and 1460 1180                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-c-2 and 1300 1125                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-c-2 and 1095  862                                         0.05% of compound 2-g-1                                                       0.05% of compound 1-c-2 and  820  775                                         0.05% of compound 2-g-2                                                       0.05% of compound 1-c-2 and 1125 1037                                         0.05% of compound 2-k-2                                                       0.05% of compound 1-c-2 and 1155  942                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-c-2 and 1900 1470                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-c-2 and 1400 1290                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-c-2 and 1430 1265                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-f-1 and 1220  925                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-f-1 and  985  735                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-f-1 and 1220 1040                                         0.05% of compound 2-b-1                                                       0.05% of compound 1-f-1 and 1020  945                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-f-1 and 1095  875                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-f-1 and  910  820                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-f-1 and  785  637                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-f-1 and 1630 1165                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-f-1 and 1085  985                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-f-1 and 1230  960                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-b-1 and 1400  965                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-b-1 and  905  775                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-b-1 and 1005  985                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-b-1 and  965  772                                         0.05% of compound 2-k-2                                                       0.05% of compound 1-b-1 and  850  677                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-b-1 and 1760 1205                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-b-1 and 1370 1025                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-b-1 and 1440 1000                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-a-1 and 1300 1122                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-a-1 and 1160 1052                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-a-1 and 1180  997                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-a-1 and  860  735                                         0.05% of compound 2-g-1                                                       0.05% of compound 1-a-1 and  870  815                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-a-1 and 1640 1342                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-a-1 and 1250 1162                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-d-2 and  600  565                                         0.05% of compound 2-k-2                                                       0.05% of compound 1-d-2 and  517  470                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-d-2 and 1190  997                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-d-2 and  875  792                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-k-1 and 1125 1002                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-k-1 and 1590 1242                                         0.05% of compound 2-e-1                                                       0.05% of compound 1-g-2 and  422  407                                         0.05% of compound 2-g-1                                                     ______________________________________                                    

Example 3

Light stabilization in low-density polyethylene films.

100 parts of low-density (density=0.918 g/cm³) polyethylene powder arehomogenized with 0.03 part of octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and with the lightstabilizers indicated in Table 3 in a Brabender plastograph at 180° C.for 10 minutes. The composition thus obtained is removed from thecompounder as rapidly as possible and compressed in a press to give asheet with a thickness of 2-3 mm. A piece of the resultant greenpress-moulding is cut out and pressed between two high-gloss hardaluminium foils for 6 minutes at 170° C. under using a laboratoryhydraulic press to give a film with a thickness of 0.2 mm, which isimmediately cooled in a water-cooled press. Sections each measuring 60mm×25 mm are then punched out of this 0.2 mm film and exposed to fuminghydrochloric acid for 24 hours. This is regarded as a simulation of theeffect of halogen containing compounds such as certain pesticides orflame retardants.

The samples are then exposed in a WEATHER-OMETER Ci 65 (black paneltemperature 63±2° C., no irrigation). The test specimens are removedfrom the exposure apparatus at regular intervals and tested for theircarbonyl content in an IR spectrometer. The increase in the carbonylextinction on exposure is a measure of the photo oxidative degradationof the polymer and is known from experience to be associated with adeterioration in the mechanical properties.

The time (T₀.2 measured) needed to reach a carbonyl extinction of 0.2 isshown in Table 3.

The synergistic effect is determined by a comparison of the calculatedT₀.2 value with the measured T₀.2 value as shown in Example 1.

                  TABLE 3                                                         ______________________________________                                        Light stabilization action in low-density polyethylene films.                                        T.sub.0.2 measured                                                                      T.sub.0.2 calculaLed                           Light stabilizer in hours in hours                                          ______________________________________                                        None                215                                                         0.1% of compound 1-b-1 2620                                                   0.1% of compound 1-a-1 1560                                                   0.1% of compound 1-c-2 4680                                                   0.1% of compound 1-c-1 6760                                                   0.1% of compound 2-m-1 about 215                                              0.1% of compound 2-d-1 2920                                                   0.1% of compound 2-b-1 2020                                                   0.1% of compound 2-d-2 3060                                                   0.1% of compound 2-f-1 2740                                                   0.1% of compound 2-i-1 3000                                                   0.1% of compound 2-g-1 1520                                                   0.1% of compound 2-g-2  740                                                   0.1% of compound 2-k-2 1840                                                   0.1% of compound 2-k-1 2000                                                   0.1% of compound 2-a-4 2400                                                   0.1% of compound 2-a-3 2440                                                   0.05% of compound 1-b-1 and 1620 1417                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-b-1 and 3220 2770                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-b-1 and 2920 2840                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-b-1 and 3200 2680                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-b-1 and 2900 2810                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-b-1 and 2400 2070                                         0.05% of compound 2-g-1                                                       0.05% of compound 1-b-1 and 2400 2230                                         0.05% of compound 2-k-2                                                       0.05% of compound 1-b-1 and 2640 1810                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-b-1 and 3300 2510                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-b-1 and 3000 2530                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-a-1 and 4160 2310                                         0.05% of compound 2-d-2                                                       0.05% of compound 1-a-1 and 4560 2150                                         0.05% of compound 2-f-1                                                       0.05% of compound 1-a-1 and 2940 2280                                         0.05% of compound 2-i-1                                                       0.05% of compound 1-a-1 and 1970 1540                                         0.05% of compound 2-g-1                                                       0.05% of compound 1-a-1 and 1360 1150                                         0.05% of compound 2-g-2                                                       0.05% of compound 1-a-1 2820 1700                                             0.05% of compound 2-k-2                                                       0.05% of compound 1-a-1 and 2460 1780                                         0.05% of compound 2-k-1                                                       0.05% of compound 1-a-1 and 3300 1980                                         0.05% of compound 2-a-4                                                       0.05% of compound 1-a-1 and 3760 2000                                         0.05% of compound 2-a-3                                                       0.05% of compound 1-c-2 and 4560 3800                                         0.05% of compound 2-d-1                                                       0.05% of compound 1-c-2 and 4000 3350                                         0.05% of compound 2-b-1                                                       0.05% of compound 1-c-1 and 4680 3487                                         0.05% of compound 2-m-1                                                       0.05% of compound 1-c-1 and 5040 4390                                         0.05% of compound 2-b-1                                                     ______________________________________                                    

What is claimed is:
 1. A stabilizer mixture comprising a first componentI-b), I-c), I-d) or I-l) and a second component II-b), II-c), II-d) orII-l), wherecomponent I-b) is at least one compound of the formula II-1##STR125## in which R₃ and R₇ independently of one another are hydrogenor C₁ -C₁₂ alkyl,R₄, R₅ and R₆ independently of one another are C₂ -C₁₀alkylene and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of oneanother are a group of the formula III-1 ##STR126## in which R₈ ishydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, C₁ C₄ alkyl-substituted C₅-C₁₂ cycloalkyl, phenyl --OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl,C₇ -C₉ phenylalkyl, C₇ -C₉ phenylalkyl which is substituted on thephenyl radical by --OH and/or C₁ -C₁₀ alkyl, or is a group of theformula IV-1 ##STR127## and R₉ and R₁₀ independently of one another arehydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or C₁ -C₄ alkyl-substitutedC₅ -C₁₂ cycloalkyl; component I-c) is at least one compound of theformula V-1 ##STR128## in which X₉, X₁₀ and X₁₁ independently of oneanother are a group of the formula III-1; component I-d) is at least onecompound of the formula VI-1 ##STR129## in which R₁₁, R₁₃, R₁₄ and R₁₅independently of one another are hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl, phenyl, --OH--and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇ -C₉ phenylalkyl, C₇ -C₉phenylalkyl which is substituted on the phenyl radical by --OH and/or C₁-C₁₀ alkyl, or are a group of the formula IV-1,R₁₂ is C₂ -C₁₈ alkylene,C₅ -C₇ cycloalkylene or C₁ -C₄ alkylenedi(C₅ -C₇ cycloalkylene), or theradicals R₁₁, R₁₂ and R₁₃, together with the nitrogen atoms to whichthey are attached, form a 5- to 10-membered heterocyclic ring, or R₁₄and R₁₅, together with the nitrogen atom to which they are attached,form a 5- to 10-membered heterocyclic ring, n₂ is a number from 2 to 50and at least one of the radicals R₁₁, R₁₃, R₁₄ and R₁₅ is a group of theformula IV-1; component I-l) is at least one compound of the formulaXIV-1 ##STR130## in which X₁₂, X₁₃ and X₁₄ independently of one anotherare a group of the formula XV-1 ##STR131## in which A is a group of theformula III-1; component II-b) is at least one compound of the formulaII-2 ##STR132## in which A₃ and A₇ independently of one another arehydrogen or C₁ -C₁₂ alkyl,A₄, A₅ and A₆ independently of one another areC₂ -C₁₀ alkylene and T₁, T₂, T₃, T₄, T₅, T₆, T₇ and T₈ independently ofone another are a group of the formula III-2 ##STR133## in which A₈ ishydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅-C₁₂ cycloalkyl, phenyl, --OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl,C₇ -C₉ phenylalkyl, C₇ -C₉ phenylalkyl which is substituted on thephenyl radical by --OH and/or C₁ -C₁₀ alkyl, or is a group of theformula IV-2 ##STR134## and A₉ and A₁₀ independently of one another arehydrogen, C₁ -C₈ alkyl, O, --CH₂ CN, C₃ -C₆ alkenyl, C₇ -C₉ phenylalkylor C₇ -C₉ phenylalkyl which is substituted on the phenyl radical by C₁-C₄ alkyl; component II-c) is at least one compound of the formula V-2##STR135## in which T₉, T₁₀ and T₁₁ independently of one another are agroup of the formula III-2; component II-d) is at least one compound ofthe formula VI-2 ##STR136## in which A₁₁, A₁₃, A₁₄ and A₁₅ independentlyof one another are hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄alkyl-substituted C₅ -C₁₂ cycloalkyl, phenyl, --OH-- and/or C₁ -C₁₀alkyl-substituted phenyl, C₇ -C₉ phenylalkyl, C₇ -C₉ phenylalkyl whichis substituted on the phenyl radical by --OH and/or C₁ -C₁₀ alkyl, orare a group of the formula IV-2,A₁₂ is C₂ -C₁₈ alkylene, C₅ -C₇cycloalkylene or C₁ -C₄ alkylenedi(C₅ -C₇ cycloalkylene), or theradicals A₁₁, A₁₂ and A₁₃, together with the nitrogen atoms to whichthey are attached, form a 5- to 10-membered heterocyclic ring, or A₁₄and A₁₅, together with the nitrogen atom to which they are attached,form a 5- to 10-membered heterocyclic ring, b₂ is a number from 2 to 50and at least one of the radicals A₁₁, A₁₃, A₁₄ and A₁₅ is a group of theformula IV-2; component II-l) is at least one compound of the formulaXIV-2 ##STR137## in which T₁₂, T₁₃ and T₁₄ independently of one anotherare a group of the formula XV-2 ##STR138## in which L is a group of theformula III-2; and provided that the first stabilizer component and thesecond stabilizer component are not the same.
 2. A stabilizer mixtureaccording to claim 1, in which R₉, or R₁₀, independently of one anotherare C₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl or methyl-substituted C₅ -C₈cycloalkyl.
 3. A stabilizer mixture according to claim 1, in which R₉ orR₁₀, independently of one another are methyl, octyl or cyclohexyl.
 4. Astabilizer mixture according to claim 1, in which A₉, or A₁₀,independently of one another are hydrogen or methyl.
 5. A stabilizermixture according to claim 1, in whichR₃ and R₇ independently of oneanother are hydrogen or C₁ -C₄ alkyl, R₄, R₅ and R₆ independently of oneanother are C₂ -C₆ alkylene, R₈ is hydrogen, C₁ -C₆ alkyl, C₅ -C₈cycloalkyl, methyl-substituted C₅ -C₈ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV-1; R₁₁, R₁₃, R₁₄ and R₁₅independently of one another are hydrogen, C₁ -C₈ alkyl, C₅ -C₈cycloalkyl, methyl-substituted C₅ -C₈ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV-1, or the radicals R₁₄ and R₁₅,together with the nitrogen atom to which they are attached, form a6-membered heterocyclic ring, R₁₂ is C₂ -C₁₀ alkylene and n₂ is a numberfrom 2 to 25; R₃₆, R₃₈, R₃₉ and R₄₀ independently of one another are C₁-C₄ akylene, R₃₇ is a direct bond and n₇ is a number from 1 to
 25. 6. Astabilizer mixture according to claim 1, in whichcomponent I-b) is atleast one compound of the formula II-1-b ##STR139## in which R₉ ismethyl, octyl or cyclohexyl; component I-c) is at least one compound ofthe formula V-1-c ##STR140## in which R₉ is as defined above; componentI-d) is at least one compound of the formula VI-1-d-1, VI-1-d-2 orVI-1-d-3 ##STR141## in which R₁₀ is as defined for R₉ and n₂ is a numberfrom 2 to 25; component I-l) is at least one compound of the formulaXIV-l-1 ##STR142## in which R₉ is as defined above.
 7. Stabilizermixture according to claim 1, in whichA₃ and A₇ independently of oneanother are hydrogen or C₁ -C₄ alkyl, A₄, A₅ and A₆ independently of oneanother are C₂ -C₆ alkylene, A₈ is hydrogen, C₁ -C₆ alkyl, C₅ -C₈cycloalkyl,methyl-substituted C₅ -C₈ cycloalkyl, phenyl,C₇ -C₉phenylalkyl or a group of the formula IV-2; A₁₁, A₁₃, A₁₄ and A₁₅independently of one another are hydrogen,C₁ -C₈ alkyl, C₅ -C₈cycloalkyl, methyl-substituted C₅ -C₈ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV-2, or the radicals A₁₄ and A₁₅,together with the nitrogen atom to which they are attached, form a6-membered heterocyclic ring, A₁₂ is C₂ -C₁₀ alkylene and b₂ is a numberfrom 2 to
 25. 8. A stabilizer mixture according to claim 1, inwhichcomponent II-b) is at least one compound of the formula II-2-b##STR143## in which A₉ is hydrogen or methyl; component II-d) is atleast one compound of the formula VI-2-d-1, VI-2-d-2 or VI-2-d-3##STR144## in which A₁₀ is as defined for A₉ and b₂ is a number from 2to
 25. 9. A composition comprising an organic material sensitive tooxidative, thermal or light-induced degradation and a stabilizer mixtureaccording to claim
 1. 10. A composition according to claim 9, in whichthe organic material is a polyolefin.
 11. A composition according toclaim 9, in which the organic material is polyethylene, polypropylene ora copolymer of polyethylene or polypropylene.